Real-Space Observation of Quantum Tunneling by a Carbon Atom: Flipping Reaction of Formaldehyde on Cu(110).

We present a direct observation of carbon-atom tunneling in the flipping reaction of formaldehyde between its two mirror-reflected states on a Cu(110) surface using low-temperature scanning tunneling microscopy (STM). The flipping reaction was monitored in real time, and the reaction rate was found to be temperature independent below 10 K. This indicates that this reaction is governed by quantum mechanical tunneling, albeit involving a substantial motion of the carbon atom (∼1 Å). In addition, deuteration of the formaldehyde molecule resulted in a significant kinetic isotope effect ( R/ R ≈ 10). The adsorption structure, reaction pathway, and tunneling probability were examined by density functional theory calculations, which corroborate the experimental observations.